Copolymers of tetra-allyl pentaerythritol



Patented Feb. 22, 1949 COPOLYMERS OF TETRA-ALLYL PENTAERYTHRITOL Lee T.Smith, Philadelphia, Pa., assignor to the United States of America asrepresented by the Secretary of Agriculture No Drawing. ApplicationApril 26, 1946, Serial No. 665,039

6 Claims. (Cl. 260-857) (Granted under the act of March 3, 1883, asamended April 30, 1928; 370 O. G. 757) This application is made underthe act of March 3, 1883, as amended by the act of April 30, 1928, andthe invention herein described, if patented, may be manufactured andused by or for the Government of the United States of America forgovernmental purposes without the payment to me of any royalty thereon.

This invention relates to the copolymerization of allyl ethers ofpolyhydrie alcohols such as diallyl ethylene glycol and allyl glycerine,and allyl ethers of sucrose, starch, cellulose, and other carbohydrateswith unsaturated compounds such as the acrylates, the methacrylates,styrene, dienes, vinyl derivatives, and allyl esters, such as forinstance allyl phthalate or allyl succinate.

Although the polymerization of allyl ethers such as those mentionedabove is not catalyzed appreciably by use of organic and inorganicperoxides and per-compounds such as benzoyl peroxide and potassiumperchlorate or persulfate, copolymerization is effected between theallyl ethers and the unsaturated compounds of the type set forth abovewhen mixtures of the allyl ethers and other unsaturated materials areallowed to stand, or when the mixtures are heated with or withoutperoxide, persulfate, or perchlorate catalysts.

In order to form copolymers with desirable properties, the number ofallyl groups per molecule must, in general, be two or more.Polyfunctlonal alcohols containing two or more hydroxyl groups should,in general, have an average degree of allylatlon of two, so that thecorresponding allyl ether would form copolymers of the desired kind.However, mixtures having an average degree of allylation less than twoare still satisfactory, providing a sufficient number of bl-functionalor polyfunctional molecules are in the mixture.

The copolymerizatlon may be brought about in mass by simply mixing thetwo monomers together, in solution in a common solvent, such as acetone,ethyl acetate, and so forth, or by making a water emulsion of the twomonomers and then bringing about copolymerlzation with or without theaid of heat and catalysts. In addition, partially polymerized resins canbe dissolved in a solution of polyallyl ethers which are already'resins, such as allyl starch and allyl cellulose, and after applicationas a coating, an insoluble, in- Iusible film is formed on baking.

These copolymerized materials have properties which differ from thecorresponding polymers from each of the monomers used. In general,colorless and transparent resins of the insoluble,

infusible type are formed. The properties 01 the final product will varyfrom a soft, rubbery mass to a hard, brittle material, depending onwhich allyl ether and which other unsaturated monomer is used, the ratioof the materials used,

and the conditions under which the copolymerlzation is carried out.These copolymers have wide and extensive uses varying from protectivecoatings to molded articles.

The following examples, in which the proportions are in parts by weight,are given by way of illustration and not in limitation.

Example I 10 parts of tetra-allyl pentaerythritol, 90 parts of methylmethacrylate, and one part of benzoyl peroxide were thoroughly mixed andallowed to stand at room temperature. A hard, transparent, colorlessresin resulted, which swells in acetone but does not dissolve.

Example I] 20 parts of tetra-allyl pentaerythritol, parts of methylmethacrylate, and one part of benzoyl peroxide were mixed thoroughly andallowed to stand at room temperature. The resulting copolymer was softand tacky, and it swelled in oeganic solvents such as dioxane oracetone.

Example III 20 parts of allyl starch, 20 parts of vinyl acetate, and 0.5part of benzoyl peroxide were thoroughly mixed and heated under refluxat C. for 12 hours. The resulting copol er was hard and insoluble inorganic solvents.

Example IV Example V 20 parts of allyl starch, 20 part of styrene. and0.5 part of benzoyl peroxide were thoroughly mixed and allowed to standat room temperature in a closed container. The copolymer product washard and tough; it swells slightly in acetone.

Example VI 50 parts of tetra-allyl pentaerythritol, 50 parts of methylmethacrylate, and 1 part of benzoyl peroxide were mixed thoroughly andheated at 55 C. The resulting product was transparent,

colorless, and tough, and swelled but did not dissolve in acetone.

Example VII parts of tetra-allyl pentaerythritol, 80 *parts of vinylacetate, and 1 part of benzoyl peroxide were mixed thoroughly andallowed to stand at room temperature. The resulting copolymer was softand crumbly and swelled but did not dissolve in organic solvents.Cross-reference is made to Nichols-and Smith application 518,979, filedJanuary 20, 1944 now abandoned, for other types of allyl compounds thatmay be employed, for example, allyl starches. Among the types of allylcellulose or allyl starch that may be employed in the above examples arethose described in Hamilton and Nichols application 518,976, filedJanuary 20, 1944, now United States Patent No. 2,406,369.

Dienes such as butadiene, chlorbutadiene, an cyclopentadiene, may beemployed. Having thus described my invention, I claim: 1. A resincomprising a copolymer of 10 to 50 parts of tetra-allyl pentaerythritoland 90 R 50 parts of methyl methacrylate.

2. A resin comprising a copolymer of 10 to 50 parts of tetra-allylpentaerythritol and 90 to 50 parts of vinyl acetate.

3. A resin comprising a copolymer of 10 to' 50 parts of a poly-allyletherof a polyhydric alcohol, which alcohol has no functional groupother than hydroxyl, and 90 to 50 parts of a monomeric polymerizableolefinic compound of the group consisting of acrylic acid esters,methacrylic esters, vinyl esters, and allyl esters having the linkage 4.A resin comprising a copolymer of 10 to 50 parts of tetra-allylpentaerythrltol and 90 to 50 parts of a monomeric polymerizableolefini'c coinpound of the group consisting of acrylic acid esters,methacrylic esters, vinyl esters, and allyl esters having the linkage I5. A process of making a copolymer, comprising reacting 10 to parts oftetra-allyl pentaerythritol and to 50 parts of a monomeric polymerizableolefinic compound of the group consisting of acrylic acid esters,methacrylic esters, vinyl esters, and allyl esters havingthe linkage(DEF?- in the presence of a polymerization catalyst of the groupconsisting 'of organic and inorganic '"per compounds.

6. A process of making a copolymer, comprising reacting 10 to 50 partsof poly-allyl ether of polyhydrlc alcohol, which alcohol has nofunctional group other than hydroxyl, and 90 to 50' parts of a monomericpolymerizable oleflnic compound of the group consisting of acrylic acidesters, methacrylic esters, vinyl esters, and allyl esters having thelinkage REFERENCES CITED The following references are of record in thefile of this patent:

UNITED STATES PATENTS Number Name Date I 2,037,740 Salzberg Apr. 21,1936 2,386,999 Adelson et a1." Oct. 16, 1945 OTHER REFERENCES NicholsJr. a 9.1., Article in Oiflcial Digest Paint and Varnish ProductionClubs. March 1945, pp. 111-123. A

